Pipecolic acid-catalyzed direct asymmetric Mannich reactions

被引：92

作者：

Cheong, PHY ^{[1
]}

Zhang, HL

Thayumanavan, R

Tanaka, F

Houk, KN

Barbas, CF

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[2] Scripps Res Inst, Skaggs Inst Chem Biol, La Jolla, CA 92037 USA

[3] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA

[4] Scripps Res Inst, Dept Biol Mol, La Jolla, CA 92037 USA

来源：

ORGANIC LETTERS | 2006年 / 8卷 / 05期

关键词：

D O I：

10.1021/ol052861o

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Mannich reactions between aldehydes and N-p-methoxyphenyl-protected alpha-imino ethyl glyoxylate have been performed using (S)-pipecolic acid as catalyst. The reactions give both syn- and ant products (dr = 1.4-2:1) with high enantioselectivities (> 98% ee). In contrast, (S)proline-catalyzed reactions give mainly syn-products with high enantioselectivities. Computational studies reveal that the energetic preference between the transition structures involving the s-cis-enamine and the s-trans-enamine is smaller for the pipecolic acid as compared to proline, yielding the (2S,3R)-anti and the (2S,3S)-syn Mannich product in nearly equal amounts.

引用

页码：811 / 814

页数：4

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